Coating composition for dielectric insulating film, dielectric insulating film prepared therefrom, and electric or electronic device comprising the same

ABSTRACT

The present invention relates to a coating composition for a dielectric insulating film comprising a) an organosiloxane polymer, b) first metal ions selected from the group consisting of Rb ions, Cs ions, and a mixture thereof, and c) an organic solvent, in which the first metal ions are comprised at 1 to 200 ppm based on the weight of the composition, a dielectric insulating film prepared therefrom, and an electric or electronic device comprising the same. A dielectric insulating film prepared from the coating composition of the present invention has an improved dielectric constant and superior mechanical strength and electric properties.

CROSS REFERENCES TO RELATED APPLICATION

This application claims priority to and the benefit of Korean PatentApplication No. 10-2005-0021977 filed in the Korean Industrial PropertyOffice on Mar. 16, 2005, the entire contents of which are incorporatedhereinto by reference.

FIELD OF THE INVENTION

The present invention relates to a coating composition for a dielectricinsulating film, a dielectric insulating film prepared therefrom, and anelectric or electronic device comprising the same, and more particularlyto a coating composition for a dielectric insulating film havingsuperior mechanical strength and electric properties while having a lowdielectric constant, a dielectric insulating film prepared therefrom,and an electric or electronic device comprising the same.

BACKGROUND OF THE INVENTION

As semiconductor devices become more integrated, and consequently themetal wiring pitches decrease, such problems as propagation delay,crosstalk noise, and power dissipation are causing concern.

To solve these problems, reducing the RC delay can initially beconsidered. For this purpose, resistance of the metal wiring materialand conductance between each metal wire are reduced. In general, use ofcopper (Cu) which has good electric conductivity as a metal wiringmaterial and a highly insulating material between the metal wires areknown to be good for the purpose.

Most currently used insulating are SiO₂ based materials, having adielectric constant of 4.0. Recently, materials having a dielectricconstant of 3.0 have become commercially available. Efforts are beingmade to reduce the constant to below 2.2 or 2.0 in the long term.

As conventional ways of reducing the dielectric constant to or below2.5, there are a method of introducing a pore generating material into alow-dielectric matrix resin, curing it, and removing the material toobtain a porous dielectric insulating film, a method of hydrolyzing asilane compound in the presence of a base catalyst and polymerizing itto obtain a porous film, and so forth. Although low-dielectricinsulating films obtained by these methods have a dielectric constant of2.5 or less, mechanical strength decreases significantly and electricproperties worsen because of the presence of pores. Thus, improvement ofphysical properties is required for semiconductors.

Besides having good dielectric and mechanical properties, a coatingcomposition for a dielectric insulating film used in a semiconductordevice should have particulate or metallic impurities below a givenlevel. If particles or metal ions are present in the dielectricinsulating film composition, productivity may decrease.

Also, if metals such as Na, K, Ca, Fe, Cu, Ni, Mg, and Zn or their ionsare present in the dielectric insulating film composition, electricproperties of the resultant dielectric insulating film may be poor.Especially, such metal ions as Na⁺ and K⁺ should be controlled to belowa given level, because they diffuse fast and may cause a fatal effect onthe performance of the gate device.

SUMMARY OF THE INVENTION

The present invention was made in consideration of the above-mentionedproblems, and it is an object of the invention to provide a coatingcomposition for a dielectric insulating film comprising specific metalions and thus offering a low dielectric constant and superior mechanicalstrength and electric properties to a dielectric insulating film.

It is another object of the invention to provide a dielectric insulatingfilm prepared from the dielectric insulating film composition and whichthus has a low dielectric constant and superior mechanical strength andelectric properties.

It is still another object of the invention to provide an electric orelectronic device comprising the dielectric insulating film.

In order to attain the objects, the present invention provides a coatingcomposition for a dielectric insulating film comprising a) anorganosiloxane polymer; b) a first metal ions selected from the groupconsisting of Rb ions, Cs ions, and a mixture thereof; and c) an organicsolvent, where the first metal ions are comprised at 1 to 200 ppm basedon the weight of the composition.

The invention also provides a dielectric insulating film prepared fromthe coating composition for a dielectric insulating film and comprisingmetal ions selected from the group consisting of Rb ions, Cs ions, and amixture thereof.

The invention further provides an electric or electronic devicecomprising the dielectric insulating film.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereunder is given a detailed description of the present invention.

The present inventors worked on a dielectric insulating film having alow dielectric constant and superior mechanical and electric propertieswhile containing fewer metals, such as Na, K, Ca, Fe, Cu, Ni, Mg, andZn, and ions thereof. In doing so, they found that a coating compositionfor a dielectric insulating film including a specific amount of Rb ions,Cs ions, or a mixture thereof facilitates curing of the dielectricinsulating film and increases cross-linkage density of the dielectricinsulating film, thereby improving the mechanical strength, dielectricproperty, electric properties, etc., of the dielectric insulating film.

In this specification, Rb ions, Cs ions, or a mixture thereof isreferred to as the first metal ions, and the other metal ions excludingthe Rb ions or the Cs ions, such as Na, K, Ca, Fe, Cu, Ni, Mg, or Znions, is referred to as the second metal ions.

In general, in the manufacturing process of semiconductor devices, thesecond metal ions may be included above a certain level when makingcopper wiring and during barrier film processing and dielectricinsulating film manufacturing. Also, it may be included above a certainlevel when manufacturing the coating composition for a dielectricinsulating film because of the organosiloxane polymer source, solvent,reactor, and so forth.

If a coating composition containing the second metal ions is preparedinto a dielectric insulating film, the electric properties of thedielectric insulating film may be not good. In particular, the Na⁺ ionsand the K⁺ ions may cause a fatal effect on the gate devicecharacteristics because of a very fast diffusion rate. Thus, theircontent is strictly limited in semiconductor manufacturing processes.

However, if a coating composition not containing the second metal ionsis prepared into a dielectric insulating film, the dielectric property,mechanical strength, and electric properties become poor.

The coating composition for a dielectric insulating film in accordancewith the present invention comprises a) an organosiloxane polymer, b)first metal ions selected from the group consisting of Rb ions, Cs ions,and a mixture thereof, and c) an organic solvent.

The organosiloxane polymer may be any one polymerized from a silanecompound or a silane oligomer, however an organosiloxane polymerpolymerized from at least one silane compound selected from the groupconsisting of a) at least one monomer selected from the group consistingof the compounds represented by Formula 1 and Formula 2 below, b) adimer prepared from the monomer, and c) an oligomer prepared from themonomer, the dimer, or a mixture thereof, is more preferable in terms ofdielectric property and mechanical strength.SiR¹ _(p)R² _(4-p)   (1)

where

R¹ is hydrogen, an aryl, a vinyl, an allyl, a C₁-C₄ linear or branchedalkyl substituted with fluorine, or a C₁-C₄ linear or branched alkyl notsubstituted with fluorine;

R² is a C₁-C₄ linear or branched alkoxy, acetoxy, or chlorine; and

p is an integer of 1 or 2,R³ _(q)R⁴ _(3-q)Si-M-SiR⁵ _(r)R⁶ _(3-r)   (2)

where

each of R³ and R⁵ is, independently, hydrogen, fluorine, an aryl, avinyl, an allyl, a C₁-C₄ linear or branched alkyl substituted withfluorine, or a C₁-C₄ linear or branched alkyl not substituted withfluorine;

each of R⁴ and R⁶ is, independently, a C₁-C₄ linear or branched alkoxy,an acetoxy, or chlorine;

M is a C₁-C₆ alkylene, or a phenylene; and

each of q and r is an integer of 0 to 2.

The organosiloxane polymer preferably has a weight-average molecularweight, in terms of equivalent polystyrene molecular weight, of at least500, and is preferably in the range of 500 to 1,000,000. If theweight-average molecular weight of the organosiloxane polymer is lessthan 500, the coating property of the dielectric insulating film mayworsen.

The organosiloxane polymer may be prepared by mixing a silane compoundpolymerized from at least one selected from the group consisting of i)at least one monomer selected from the group consisting of the compoundsrepresented by Formula 1 and Formula 2, ii) a dimer prepared from themonomer, and iii) an oligomer prepared from the monomer, the dimer, or amixture thereof with a catalyst and water, and then hydrolyzing andcondensing the silane compound.

The hydrolysis and condensation may proceed by adding an organicsolvent, if necessary. Preferably, the hydrolysis and condensation areperformed in the presence of an organic solvent for convenience ofmolecular weight control of the organosiloxane polymer to bepolymerized.

In the preparation of the organosiloxane polymer, any organic solventthat does not affect the hydrolysis or condensation of the silanecompound may be used, however, at least one selected from the groupconsisting of an aliphatic hydrocarbon solvent, an aromatic hydrocarbonsolvent, an alcohol solvent, a ketone solvent, an ether solvent, anester solvent, and an amide solvent is preferable.

To be specific, at least one organic solvent selected from the groupconsisting of a) at least one aliphatic hydrocarbon solvent selectedfrom the group consisting of n-pentane, i-pentane, n-hexane, i-hexane,2,2,4-trimethylpentane, cyclohexane, and methylcyclohexane, b) at leastone aromatic hydrocarbon solvent selected from the group consisting ofbenzene, toluene, xylene, trimethylbenzene, ethylbenzene, andmethylethylbenzene, c) at least one alcohol solvent selected from thegroup consisting of methyl alcohol, ethyl alcohol, n-propanol,i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol,4-methyl-2-pentanol, cyclohexanol, methylcyclohexanol, and glycerol, d)at least one ketone solvent selected from the group consisting ofmethylethylketone, methylisobutylketone, diethylketone, methyln-propylketone, methyl n-butylketone, cyclohexanone,methylcyclohexanone, and acetylacetone, e) at least one ether solventselected from the group consisting of tetrahydrofuran,2-methyltetrahydrofuran, ethyl ether, n-propylether, isopropylether,diglyme, dioxin, dimethyldioxin, ethylene glycol monomethyl ether,ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propyleneglycol monomethyl ether, and propylene glycol dimethyl ether, f) atleast one ester solvent selected from the group consisting of diethylcarbonate, methyl acetate, ethyl acetate, ethyl lactate, ethylene glycolmonomethyl ether acetate, propylene glycol monomethyl ether acetate, andethylene glycol diacetate, and g) at least one amide solvent selectedfrom the group consisting of N-methylpyrrolidone, formamide,N-methylformamide, N-ethylformamide, N,N-dimethylacetamide, andN,N-diethylacetamide is preferable.

The catalyst used in the hydrolysis and condensation may be an acidcatalyst or a base catalyst. In general, an acid catalyst is preferablewhen an organic molecule or an organic polymer is processed.

The acid catalyst is not particularly limited, but at least one selectedfrom the group consisting of hydrochloric acid, nitric acid, sulfuricacid, phosphoric acid, fluoric acid, formic acid, acetic acid, propionicacid, butanoic acid, pentanoic acid, hexanoic acid, monochloroaceticacid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid,oxalic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid,citric acid, maleic acid, oleic acid, methylmalonic acid, adipic acid,p-aminobenzoic acid, and p-toluenesulfonic acid is preferable.

The base catalyst is also not particularly limited, but at least oneselected from the group consisting of an alkali metal compound, ammoniawater, an organic amine, and a quaternary ammonium compound ispreferable.

The addition amount of the catalyst is not particularly limited, but isdetermined depending on the kind of the catalyst and the silanecompound.

The water used along with the catalyst is added to hydrolyze the silanecompound. Preferably, the water is used at 1 to 30 moles, morepreferably at 2 to 20 moles, per 1 mole of hydrolysable functionalgroups of the silane compound. If the water content is below 1 mole permole of hydrolysable functional groups of the silane compound,hydrolysis and condensation may be insufficient, and the resultantdielectric insulating film will not have good dielectric and mechanicalproperties. Otherwise, if the water content exceeds 30 moles per mole ofhydrolysable functional groups of the silane compound, phase separationmay occur during hydrolysis and condensation, thereby causingnon-uniform reaction, and the coating property tends to become poor.

Water may be added incrementally or continuously. The catalyst may bemixed in the organic solvent in advance, or may be added after beingdissolved or dispersed in water.

Preferably, the hydrolysis and condensation of the organosiloxanepolymer are performed at 0 to 100° C.

The first metal ions may be added along with the organosiloxane polymerand the organic solvent included in a metal salt comprising Rb ions, Csions, or a mixture thereof.

The first metal ions are preferably comprised at 1 to 200 ppm, morepreferably at 5 to 100 ppm, based on the weight of the coatingcomposition for a dielectric insulating film. If the content of thefirst metal ions is below 1 ppm, facilitation of curing of theorganosiloxane polymer, a matrix resin, is only slight, and thusmechanical strength, electric properties, and the dielectric property ofthe dielectric insulating film become poor. Otherwise, if it exceeds 200ppm, no further property improvement is obtained and storage stabilitybecomes poor, which may cause worsening of the dielectric and electricproperties of the dielectric insulating film.

In the present invention, the content of the second metal ion should beas small as possible. Preferably, it is comprised at less than 0.5 ppmbased on the weight of the composition. And, preferably, the content ofNa⁺ ions and K⁺ ions is smaller than 0.1 ppm, and more preferablysmaller than 0.02 ppm. If the content of the second metal ions exceeds0.5 ppm, or if the content of Na⁺ ions and K⁺ ions exceeds 0.1 ppm,electric properties of the dielectric insulating film may be affected,and gate device characteristics may be fatally affected.

The second metal ions may be removed by a common metal ion removingmethod prior to the addition of the first metal ions. More specifically,the second metal ions may be washed off with water, or removed using anion exchange resin filter or a zeta-potential filter, and so forth.However, these examples are not limiting examples.

The organic solvent comprised in the coating composition for adielectric insulating film is not particularly limited. It may be theorganic solvent used in the preparation of the organosiloxane polymer, anew organic solvent added after the preparation of the organosiloxanepolymer, or a mixture of the two.

Preferable examples of the organic solvent are the same as the organicsolvent used in the preparation of the organosiloxane polymer, and willnot be specified here. However, among them, at least one ether solventselected from the group consisting of ethylene glycol monomethyl ether,ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propyleneglycol monomethyl ether, and propylene glycol dimethyl ether, and atlest one ester solvent selected from the group consisting of diethylcarbonate, methyl acetate, ethyl acetate, ethyl lactate, ethylene glycolmonomethyl ether acetate, propylene glycol monomethyl ether acetate, andethylene glycol diacetate are more preferable for use as the mainsolvent, considering the coating properties of the coating composition.

When the organic solvent that has been used in the preparation of theorganosiloxane polymer is used, it is preferable to remove specificorganic solvents that impair coating properties of the coatingcomposition, reaction byproducts produced during the preparation of theorganosiloxane polymer, and water, to below a specific level.

The coating composition for a dielectric insulating film of theinvention may further comprise d) a pore generating material, in orderto reduce the density of the dielectric insulating film. Preferably, thepore generating material is any organic molecule, or an organic polymerthat can be pyrolyzed at 450° C. or lower.

To take specific preferable examples, at least one organic moleculeselected from the group consisting of an aliphatic hydrocarbon, anaromatic hydrocarbon, an ether compound, an ester compound, an anhydridecompound, a carbonate compound, an acryl compound, a thioether compound,an isocyanate compound, an isocyanurate compound, a sulfone compound,and a sulfoxide compound that can be pyrolyzed at 150 to 450° C., or apolymer polymerized therefrom, and more preferably an alkylene oxidepolymer and an acrylate polymer that can be pyrolyzed at 150 to 450° C.,may be used.

The pore generating material may have an alkoxy silane functional group,at the terminal or inside the molecule that can react with theorganosiloxane polymer.

Preferably, the pore generating material has a weight-average molecularweight of 300 to 100,000, more preferably 300 to 20,000. If themolecular weight of the pore generating material is smaller than 300,pore generation may be insufficient. Otherwise, if it exceeds 100,000,compatibility with the matrix resin becomes poor, and formation ofmicropores becomes difficult.

Preferably, the pore generating material is at least one selected fromthe group consisting of a polymer or a copolymer having a linear, block,radial, or crosslinkage type of molecular structure. More preferably, itis at least one selected from the group consisting of a polymer or acopolymer having a block, radial, or crosslinkage type of molecularstructure.

The coating properties of the coating composition for a dielectricinsulating film are controlled by the solid content in the composition.Preferably, the coating composition for a dielectric insulating film hasa solid content of 2 to 60 wt %, and more preferably 5 to 40 wt %. Ifthe solid content is below 2 wt %, a sufficient film thickness cannot beattained. Otherwise, if it exceeds 60 wt %, coating properties andstorage stability become poor.

The coating composition for a dielectric insulating film may furthercomprise water for improvement of its mechanical strength and dielectricproperty. Preferably, the water is comprised at 1 to 10 wt %, and morepreferably at 2 to 7 wt %, per 100 wt % of the composition. If the watercontent is below 1 wt %, improvement of the mechanical strength anddielectric property is only slight. Otherwise, if it exceeds 10 wt %,coating properties of the dielectric insulating film become poor, sothat it is difficult to obtain a uniform dielectric insulating film.

The dielectric insulating film of the invention is prepared from thecoating composition for a dielectric insulating film by coating thecomposition on a substrate, and curing the resultant film by drying andbaking.

The substrate is not particularly limited, but a silicon wafer, a SiO₂wafer, a SiN wafer, a compound semiconductor, a glass substrate, or apolymer substrate is preferable.

Coating of the composition on the substrate may be performed byconventional liquid phase coating, preferably by spin coating, dipcoating, roll coating, or spray coating, and more preferably by spincoating, particularly when the dielectric insulating film is usedbetween multilayer circuits of a semiconductor device.

Thickness of the coat film may be controlled by the viscosity of thecomposition. In the case of spin coating, the thickness may becontrolled by adjusting the spinning rate of the spin coater.

After the composition is coated, an organosiloxane polymer dielectricinsulating film having a three-dimensional structure may be formed bydrying and baking.

Preferably, the drying is performed in the temperature range where theorganic solvent included in the coating composition can evaporate, morepreferably at 30 to 300° C. The drying process may be divided intopre-baking and soft-baking steps. In the pre-baking step, the organicsolvent included in the dielectric insulating film is slowly evaporated,and in the soft-baking step, a specific amount of the functional groupsof the organosiloxane polymer is cross-linked.

The baking process, which follows the drying process, is the lastprocess of reacting any remaining functional groups of theorganosiloxane polymer. The baking temperature may be determinedconsidering thermal stability of the organosiloxane polymer dielectricinsulating film, and characteristics of the semiconductor deviceprepared therefrom. Preferably, the baking is performed at 300° C. orabove, and more preferably at 350 to 500° C.

The drying and baking may be performed either by increasing thetemperature continuously, or by increasing the temperatureincrementally. In the case of incremental drying and baking, drying andbaking at each temperature is preferably performed for from 1 minute to5 hours.

The method of heating in the drying and baking is not particularlylimited. A hot plate, an oven, a furnace, etc., may be used for heating.The heating may be performed under an inert gas atmosphere, e.g., withnitrogen, argon, or helium, under an oxygen atmosphere, under anoxygen-containing gas atmosphere (e.g., air), in a vacuum, or under anammonia- or hydrogen-containing gas atmosphere.

The same or different heating methods may be used during the drying andbaking processes.

The dielectric insulating film prepared from the coating composition maycomprise first metal ions selected from the group consisting of Rb ions,Cs ions, and a mixture thereof, or a salt thereof, which is added tofacilitate curing of the organosiloxane polymer.

The first metal ions or the salt thereof facilitate curing of theorganosiloxane polymer, thereby reducing unreacted functional groups inthe dielectric insulating film, enhancing mechanical strength of thedielectric insulating film, and improving the dielectric and electricproperties of the dielectric insulating film.

The content of the first metal ions or the salt thereof is determined bythe content of the first metal ions comprised in the coating compositionfor a dielectric insulating film. Preferably, it is 5 to 1500 ppm, morepreferably 15 to 800 ppm, based on the weight of the dielectricinsulating film. If the content of the first metal ions is below 5 ppm,mechanical strength and electric properties of the dielectric insulatingfilm may worsen. Otherwise, if it exceeds 1500 ppm, dielectric andelectric properties of the dielectric insulating film may worsen.

Since the dielectric insulating film has a good dielectric property andsuperior mechanical and electric properties, it may be used as aninter-layer dielectric insulating film of a semiconductor device, aninter-layer dielectric insulating film of an electronic device, aprotection film of an electronic device, an inter-layer dielectricinsulating film of a multilayer wiring substrate, a protection film, oran anti-insulating film of a liquid crystal display device, gas barrierfilm, etc.

The thickness of the dielectric insulating film can vary depending onuse, and is not particularly limited, but when it is used as aninter-layer dielectric insulating film of a semiconductor device, athickness of 0.05 to 2 μm is preferable.

EXAMPLES

The following examples further illustrate the present invention indetail, but they are not to be construed as limiting the scope of theinvention.

Example 1

(Preparation of Coating Composition for a Dielectric Insulating Film)

100.0 g of methyl trimethoxysilane (MTMS) and 83.8 g oftetramethoxysilane (TMS) were added to 429 g of tetrahydrofuran, anorganic solvent. Then, 81.0 g of a 0.01 N aqueous nitric acid solutionwas slowly added thereto. Reaction was performed at room temperature(25° C.) for 30 minutes. After slowly heating to 80° C., reaction wasperformed overnight (24 hours) while heating and refluxing.

After the reaction was completed, the reaction solution was diluted withether, and washed with water until a neutral pH obtained. Magnesiumsulfate was added to completely remove water from the reaction solution,and then remaining solvent was completely removed in a vacuum oven toobtain an organosiloxane polymer. The organosiloxane polymer had aweight-average molecular weight of 3500.

The organosiloxane polymer was dissolved in propylene glycol methylether acetate to a 20 wt % solution. The solution was passed through ametal ion removal filter, so that the total metal ion content became0.05 ppm or lower based on the weight of the solution. Metal ion contentwas measured with an inductively coupled plasma-mass spectrometer(ICP-MS). The results are given in Table 1 below. TABLE 1 (Unit: ppm)Element Cu Fe K Na Ca Mg Zn Total Content 0.001 0.014 0.002 0.003 0.0160.004 0.004 0.044

30 ppm of a RbCl salt based on the weight of the solution was added tothe purified organosiloxane polymer solution, to obtain a coatingcomposition for a dielectric insulating film.

(Preparation of Dielectric Insulating Film)

The resultant coating composition for a dielectric insulating film wasspin coated on a silicon wafer to obtain a coat film, and dried bypre-baking on a hot plate at 80° C. for 1 minute, and then soft-bakingat 150° C. for 1 minute.

The dried silicon wafer was heated to 430° C. in a furnace, and curedfor 1 hour to obtain a dielectric insulating film.

Example 2 (Preparation of Coating Composition for a DielectricInsulating Film)

An organosiloxane polymer obtained in the same manner as in Example 1was dissolved in propylene glycol methyl ether acetate to aconcentration of 20 wt % to obtain an organosiloxane polymer solution.

And, a polyethylene oxide (PEO)-polypropylene oxide (PPO)-polyethyleneoxide (PEO) copolymer (triblock copolymer) having a weight-averagemolecular weight of 5,000 and a polyethylene oxide content of 30% wasdissolved in propylene glycol methyl ether acetate to a concentration of20 wt % to obtain a PEO-PPO-PEO solution.

A mixture of 1.1 g of water and 7.6 g of the PEO-PPO-PEO solution wasadded to 20 g of the prepared organosiloxane polymer solution. Themixture solution was passed through a metal ion removal filter, so thatthe total metal ion content became 0.05 ppm or lower based on the weightof the solution.

30 ppm of a RbCl salt based on the weight of the solution was added tothe purified polymer solution to obtain a coating composition for adielectric insulating film.

(Preparation of Dielectric Insulating Film)

A dielectric insulating film was prepared in the same manner as inExample 1.

Example 3

(Preparation of Coating Composition for a Dielectric Insulating Film)

A coating composition for a dielectric insulating film was prepared inthe same manner as in Example 2, except that 100 ppm of a RbCl saltbased on the mixture solution purified using a metal ion removal filterwas added to the solution.

(Preparation of Dielectric Insulating Film)

A dielectric insulating film was prepared in the same manner as inExample 1.

Example 4

(Preparation of Coating Composition for a Dielectric Insulating Film)

A coating composition for a dielectric insulating film was prepared inthe same manner as in Example 2, except that 100 ppm of a CsCl saltbased on the mixture solution purified using a metal ion removal filterwas added to the solution.

(Preparation of Dielectric Insulating Film)

A dielectric insulating film was prepared in the same manner as inExample 1.

Example 5

(Preparation of Coating Composition for a Dielectric Insulating Film)

A coating composition for a dielectric insulating film was prepared inthe same manner as in Example 2, except that 50 ppm of a RbCl salt and50 ppm of a CsCl salt based on the mixture solution purified using ametal ion removal filter was added to the solution.

(Preparation of Dielectric Insulating Film)

A dielectric insulating film was prepared in the same manner as inExample 1.

Comparative Example 1

(Preparation of Coating Composition for a Dielectric Insulating Film)

A coating composition for a dielectric insulating film was prepared inthe same manner as in Example 1, except that a RbCl salt was not addedafter purification using a metal ion removal filter.

(Preparation of Dielectric Insulating Film)

A dielectric insulating film was prepared in the same manner as inExample 1.

Comparative Example 2

(Preparation of Coating Composition for a Dielectric Insulating Film)

A coating composition for a dielectric insulating film was prepared inthe same manner as in Example 2, except that a RbCl salt was not addedafter purification using a metal ion removal filter.

(Preparation of Dielectric Insulating Film)

A dielectric insulating film was prepared in the same manner as inExample 1.

Comparative Example 3

(Preparation of Coating Composition for a Dielectric Insulating Film)

A coating composition for a dielectric insulating film was prepared inthe same manner as in Example 2, except that 0.2 ppm of a RbCl saltbased on the mixture solution purified using a metal ion removal filterwas added to the solution.

(Preparation of Dielectric Insulating Film)

A dielectric insulating film was prepared in the same manner as inExample 1.

Comparative Example 4

(Preparation of Coating Composition for a Dielectric Insulating Film)

A coating composition for a dielectric insulating film was prepared inthe same manner as in Example 2, except that 100 ppm of a ZnCl₂ saltbased on the mixture solution purified using a metal ion removal filterwas added to the solution instead of the RbCl salt.

(Preparation of Dielectric Insulating Film)

A dielectric insulating film was prepared in the same manner as inExample 1.

Comparative Example 5

(Preparation of Coating Composition for a Dielectric Insulating Film)

A coating composition for a dielectric insulating film was prepared inthe same manner as in Example 2, except that 100 ppm of a SnCl₂ saltbased on the mixture solution purified using a metal ion removal filterwas added to the solution instead of the RbCl salt.

(Preparation of Dielectric Insulating Film)

A dielectric insulating film was prepared in the same manner as inExample 1.

Comparative Example 6

(Preparation of Coating Composition for a Dielectric Insulating Film)

A coating composition for a dielectric insulating film was prepared inthe same manner as in Example 2, except that 100 ppm of a PtCl₂ saltbased on the mixture solution purified using a metal ion removal filterwas added to the solution instead of the RbCl salt.

(Preparation of Dielectric Insulating Film)

A dielectric insulating film was prepared in the same manner as inExample 1.

Comparative Example 7

(Preparation of Coating Composition for a Dielectric Insulating Film)

A coating composition for a dielectric insulating film was prepared inthe same manner as in Example 2, except that 100 ppm of a FeCl₃ saltbased on the mixture solution purified using a metal ion removal filterwas added to the solution instead of the RbCl salt.

(Preparation of Dielectric Insulating Film)

A dielectric insulating film was prepared in the same manner as inExample 1.

Comparative Example 8

(Preparation of Coating Composition for a Dielectric Insulating Film)

A coating composition for a dielectric insulating film was prepared inthe same manner as in Example 2, except that 100 ppm of a NiCl₂ saltbased on the mixture solution purified using a metal ion removal filterwas added to the solution instead of the RbCl salt.

(Preparation of Dielectric Insulating Film)

A dielectric insulating film was prepared in the same manner as inExample 1.

Comparative Example 9

(Preparation of Coating Composition for a Dielectric Insulating Film)

A coating composition for a dielectric insulating film was prepared inthe same manner as in Example 2, except that 500 ppm of a RbCl saltbased on the mixture solution purified using a metal ion removal filterwas added to the solution.

(Preparation of Dielectric Insulating Film)

A dielectric insulating film was prepared in the same manner as inExample 1. RbCl salt was deposited on the surface of the dielectricinsulating film, and it was impossible to obtain a uniform coat film.

Comparative Example 10

(Preparation of Coating Composition for a Dielectric Insulating Film)

A coating composition for a dielectric insulating film was prepared inthe same manner as in Example 2, except that 100 ppm of atetramethylammonium nitrate salt based on the mixture solution purifiedusing a metal ion removal filter was added to the solution. When storedat room temperature for 1 week, the viscosity of the solution droppedrapidly.

(Preparation of Dielectric Insulating Film)

A dielectric insulating film was prepared in the same manner as inExample 1.

[Measurement of Physical Properties of Dielectric Insulating Film]

The dielectric constant, mechanical strength, and leakage current weremeasured for the dielectric insulating films prepared in Examples 1 to5, and Comparative Examples 1 to 10. Measurements were made as follows.

Dielectric Constant

An MIS (metal/insulator/semiconductor) device comprising each of thedielectric insulating films prepared in Examples 1 to 5 and ComparativeExamples 1 to 10 was manufactured on a P-doped Si wafer. Measurementswere made at 1 MHz using an LCR meter (HP).

Mechanical Strength

Modulus and hardness were measured using a Nano Indenter.

Breakdown Voltage and Leakage Current)

An MIS (metal/insulator/semiconductor) device comprising each of thedielectric insulating films prepared in Examples 1 to 5 and ComparativeExamples 1 to 10 was manufactured on a P-doped Si wafer. Breakdownvoltage and leakage current were measured using a Keithley 6517electrometer.

Measurement results are shown in Table 2 below. TABLE 2 LeakageBreakdown current @ Dielectric Modulus Hardness voltage 1 MV/cm Addedmaterials constant (GPa) (GPa) (MV/cm) (A/cm²) Example 1 30 ppm RbCl2.89 14.5 1.61 5.0  ¹⁰ ⁻¹⁰ Example 2 30 ppm RbCl, 2.20 5.30 0.61 3.410⁻⁹ PEO-PPO-PEO Example 3 100 ppm RbCl, 2.18 5.89 0.65 3.6 <10⁻⁹  PEO-PPO-PEO Example 4 100 ppm CsCl, 2.20 5.59 0.62 3.9 <10⁻⁹  PEO-PPO-PEO Example 5 50 ppm RbCl + 50 ppm 2.20 5.75 0.63 3.7 <10⁻⁹  CsCl, PEO-PPO-PEO Comparative — 3.23 11.8 1.31 4.5 10⁻⁷ Example 1Comparative PEO-PPO-PEO 2.72 4.14 0.46 2.9 10⁻⁵ Example 2 Comparative0.2 ppm RbCl, 2.70 4.20 0.47 3.0 10⁻⁶ Example 3 PEO-PPO-PEO Comparative100 ppm ZnCl₂, 2.80 3.70 0.39 2.5 >10⁻⁵   Example 4 PEO-PPO-PEOComparative 100 ppm SnCl₂, 3.03 3.75 0.41 2.2 >10⁻⁵   Example 5PEO-PPO-PEO Comparative 100 ppm PtCl₂, 2.60 4.44 0.54 2.9 10⁻⁶ Example 6PEO-PPO-PEO Comparative 100 ppm FeCl₃, 3.21 4.12 0.43 2.0 >10⁻⁵  Example 7 PEO-PPO-PEO Comparative 100 ppm NiCl₂, 2.73 4.34 0.54 2.6 10⁻⁵Example 8 PEO-PPO-PEO Comparative 500 ppm RbCl, 2.34 5.60 0.62 3.1 10⁻⁷Example 9 PEO-PPO-PEO Comparative 100 ppm 2.45 3.91 0.43 3.0 10⁻⁷Example Me₄NNO₃, 10 PEO-PPO-PEO

As seen in Table 2, the dielectric insulating films prepared from thecoating compositions comprising Rb ions or CS ions, i.e., the firstmetal ions (Examples 1 to 5), had lower dielectric constants andimproved mechanical strength and electric properties compared with otherdielectric insulating films not comprising the metal ions.

The dielectric constant and mechanical properties of the dielectricinsulating films of Comparative Examples 4 to 8, which comprised themetal ions other than the Rb ions or CS ions, i.e., the second metalions, were not improved. The dielectric insulating film of ComparativeExample 10, which was prepared from the coating composition comprisingan amine (ammonium salt), which is known to facilitate curing, had poorstorage stability and mechanical strength, and the electrical anddielectric properties were not good.

While the present invention has been described in detail with referenceto the preferred embodiments, those skilled in the art will appreciatethat various modifications and substitutions can be made thereto withoutdeparting from the spirit and scope of the invention as set forth in theappended claims.

1. A coating composition for a dielectric insulating film, comprising:a) an organosiloxane polymer; b) first metal ions selected from thegroup consisting of Rb ions, Cs ions, and a mixture thereof; and c) anorganic solvent, wherein the first metal ions are comprised at 1 to 200ppm based on the weight of the composition.
 2. The coating compositionof claim 1, wherein the organosiloxane polymer is polymerized from atleast one silane compound selected from the group consisting of: a) atleast one monomer selected from the group consisting of the compoundsrepresented by Formula 1 and Formula 2 below; b) a dimer prepared fromthe monomer; and c) an oligomer prepared from the monomer, the dimer, ora mixture thereof,SiR¹ _(p)R² _(4-p)   (1) where R¹ is hydrogen, an aryl, a vinyl, anallyl, a C₁-C₄ linear or branched alkyl substituted with fluorine, or aC₁-C₄ linear or branched alkyl not substituted with fluorine, R² is alinear or branched C₁-C₄ alkoxy, acetoxy, or chlorine, and p is aninteger 1, or 2, andR³ _(q)R⁴ _(3-q)Si-M-SiR⁵ _(r)R⁶ _(3-r),   (2) where each of R³ and R⁵is, independently, hydrogen, a fluorine, an aryl, a vinyl, an allyl, aC₁-C₄ linear or branched alkyl substituted with fluorine, or a C₁-C₄linear or branched alkyl not substituted with fluorine, each of R⁴ andR⁶ is, independently, a C₁-C₄ linear or branched alkoxy, acetoxy, orchlorine; M is a C₁-C₆ alkylene, or a phenylene; and each of q and r isan integer of 0 to
 2. 3. The coating composition of claim 1, wherein thetotal content of the second metal ions which are metal ions excludingthe Rb ions or the Cs ion is 0.5 ppm or smaller.
 4. The coatingcomposition of claim 3, wherein the total content of Na ions and K ionsis 0.1 ppm or smaller.
 5. The coating composition of claim 1, whereinthe organic solvent is at least one selected from the group consistingof: a) at least one aliphatic hydrocarbon solvent selected from thegroup consisting of n-pentane, i-pentane, n-hexane, i-hexane,2,2,4-trimethylpentane, cyclohexane, and methylcyclohexane; b) at leastone aromatic hydrocarbon solvent selected from the group consisting ofbenzene, toluene, xylene, trimethylbenzene, ethylbenzene, and methylethylbenzene; c) at least one alcohol solvent selected from the groupconsisting of methyl alcohol, ethyl alcohol, n-propanol, i-propanol,n-butanol, i-butanol, sec-butanol, t-butanol, 4-methyl 2-pentanol,cyclohexanol, methylcyclohexanol, and glycerol; d) at least one ketonesolvent selected from the group consisting of methyl ethyl ketone,methyl isobutyl ketone, diethyl ketone, methyl n-propyl ketone, methyln-butyl ketone, cyclohexanone, methylcyclohexanone, and acetylacetone;e) at least one ether solvent selected from the group consisting oftetrahydrofuran, 2-methyltetrahydrofuran, ethyl ether, n-propyl ether,isopropyl ether, diglyme, dioxin, dimethyldioxin, ethylene glycolmonomethyl ether, ethylene glycol dimethyl ether, ethylene glycoldiethyl ether, propylene glycol monomethyl ether, and propylene glycoldimethyl ether; f) at least one ester solvent selected from the groupconsisting of diethyl carbonate, methyl acetate, ethyl acetate, ethyllactate, ethylene glycol monomethyl ether acetate, propylene glycolmonomethyl ether acetate, and ethylene glycol diacetate; and g) at leastone amide solvent selected from the group consisting ofN-methylpyrrolidone, formamide, N-methylformamide, N-ethylformamide,N,N-dimethylacetamide, and N,N-diethylacetamide.
 6. The coatingcomposition of claim 1, further comprising: d) a pore generatingmaterial.
 7. The coating composition of claim 6, wherein the poregenerating material is at least one organic molecule selected from thegroup consisting of an aliphatic hydrocarbon, an aromatic hydrocarbon,an ether compound, an ester compound, an anhydride compound, a carbonatecompound, an acryl compound, a thioether compound, an isocyanatecompound, an isocyanurate compound, a sulfone compound, and a sulfoxidecompound that can be pyrolyzed in the temperature range of 150 to 450°C., and a polymer polymerized therefrom.
 8. The coating composition ofclaim 7, wherein the pore generating material is a linear polymer, ablock copolymer, a radial polymer, or a crosslinkage polymer which has aweight-average molecular weight of 300 to 100,000.
 9. The coatingcomposition of claim 1, wherein a solid content of the coatingcomposition is 2 to 60 wt %.
 10. The coating composition of claim 1,further comprising: e) water.
 11. A dielectric insulating film preparedfrom a coating composition of claim 1 and comprising 5 to 1500 ppm ofthe first metal ions selected from the group consisting of Rb ions, Csions, and a mixture thereof, based on the weight of the dielectricinsulating film.
 12. The dielectric insulating film of claim 11, whereinthe coating composition comprises a organosiloxane polymer which ispolymerized from at least one silane compound selected from the groupconsisting of: a) at least one monomer selected from the groupconsisting of the compounds represented by Formula 1 and Formula 2below; b) a dimer prepared from the monomer; and c) an oligomer preparedfrom the monomer, the dimer, or a mixture thereof,SiR¹ _(p)R² _(4-p)   (1) where R¹ is hydrogen, an aryl, a vinyl, anallyl, a C₁-C₄ linear or branched alkyl substituted with fluorine, or aC₁-C₄ linear or branched alkyl not substituted with fluorine, R² is alinear or branched C₁-C₄ alkoxy, acetoxy, or chlorine, and p is aninteger 1, or 2, and R³ _(q)R⁴ _(3-q)Si-M-SiR⁵ _(r)R⁶ _(3-r),   (2)where each of R³ and R⁵ is, independently, hydrogen, a fluorine, anaryl, a vinyl, an allyl, a C₁-C₄ linear or branched alkyl substitutedwith fluorine, or a C₁-C₄ linear or branched alkyl not substituted withfluorine, each of R⁴ and R⁶ is, independently, a C₁-C₄ linear orbranched alkoxy, acetoxy, or chlorine; M is a C₁-C₆ alkylene, or aphenylene; and each of q and r is an integer of 0 to
 2. 13. Thedielectric insulating film of claim 11, wherein a total content ofsecond metal ions which are metal ions excluding the Rb ions or the Csion in the coating composition is 0.5 ppm or smaller.
 14. The dielectricinsulating film of claim 11, wherein the coating composition comprisesat least one organic solvent selected from the group consisting of: a)at least one aliphatic hydrocarbon solvent selected from the groupconsisting of n-pentane, i-pentane, n-hexane, i-hexane,2,2,4-trimethylpentane, cyclohexane, and methylcyclohexane; b) at leastone aromatic hydrocarbon solvent selected from the group consisting ofbenzene, toluene, xylene, trimethylbenzene, ethylbenzene, and methylethylbenzene; c) at least one alcohol solvent selected from the groupconsisting of methyl alcohol, ethyl alcohol, n-propanol, i-propanol,n-butanol, i-butanol, sec-butanol, t-butanol, 4-methyl 2-pentanol,cyclohexanol, methylcyclohexanol, and glycerol; d) at least one ketonesolvent selected from the group consisting of methyl ethyl ketone,methyl isobutyl ketone, diethyl ketone, methyl n-propyl ketone, methyln-butyl ketone, cyclohexanone, methylcyclohexanone, and acetylacetone;e) at least one ether solvent selected from the group consisting oftetrahydrofuran, 2-methyltetrahydrofuran, ethyl ether, n-propyl ether,isopropyl ether, diglyme, dioxin, dimethyldioxin, ethylene glycolmonomethyl ether, ethylene glycol dimethyl ether, ethylene glycoldiethyl ether, propylene glycol monomethyl ether, and propylene glycoldimethyl ether; f) at least one ester solvent selected from the groupconsisting of diethyl carbonate, methyl acetate, ethyl acetate, ethyllactate, ethylene glycol monomethyl ether acetate, propylene glycolmonomethyl ether acetate, and ethylene glycol diacetate; and g) at leastone amide solvent selected from the group consisting ofN-methylpyrrolidone, formamide, N-methylformamide, N-ethylformamide,N,N-dimethylacetamide, and N,N-diethylacetamide.
 15. The dielectricinsulating film of claim 11, wherein the coating composition furthercomprises d) a pore generating material.
 16. The dielectric insulatingfilm of claim 15, wherein the pore generating material is at least oneorganic molecule selected from the group consisting of an aliphatichydrocarbon, an aromatic hydrocarbon, an ether compound, an estercompound, an anhydride compound, a carbonate compound, an acrylcompound, a thioether compound, an isocyanate compound, an isocyanuratecompound, a sulfone compound, and a sulfoxide compound that can bepyrolyzed in the temperature range of 150 to 450° C., and a polymerpolymerized therefrom.
 17. The dielectric insulating film of claim 16,wherein the pore generating material is a linear polymer, a blockcopolymer, a radial polymer, or a crosslinkage polymer which has aweight-average molecular weight of 300 to 100,000.
 18. The dielectricinsulating film of claim 11, wherein a solid content of the coatingcomposition is 2 to 60 wt %.
 19. The dielectric insulating film of claim11, wherein the coating composition further comprises e) water.
 20. Anelectric or electronic device comprising the dielectric insulating filmof claim 11.